Diacid ester dimethyl thioether diphosphorus compounds



United States Patent 13 Claims. Cl. 260-929) ABSTRACT OF THE DISCLOSUREOrganic phosphorus diacid ester dimethyl thioethers of the formula inwhich R and R each respectively is alkyl, alkoxy, alkylamino,dialkylamino or phenyl, and X is lower carbalkoxy, aminocarbonyl,alkylaminocarbonyl, dialkylaminocarbonyl or cyano, which possesspesticidal properties, and which may be produced by conventionalmethods.

The present invention relates to thionothiol-phosphoric (-phosphonic,and -phosphinic) acid esters of the general formula having outstandinginsecticidal and acaricidal properties, as well as insecticidal andacaricidal formulations or compositions containing such acid esters, andmethods for producing and for using the same. In the above formula, Rand R represent the same or different, preferably lower, alkyl, alkoxy,alkylamino, or dialkylamino groups or phenyl radicals; and X denotes alower carbalkoxy, aminocarbonyl, alkylaminocarbonyl,dialkylaminocarbonyl or cyano group.

It is an object of the present invention to providethionothiol-phosphoric acid esters, thionothiol-phosphonic acid esters,and thionothiol-phosphinic acid esters of the foregoing type whichpossess valuable properties rendering such acid esters useful as highlyeffective insecticidal and acaricidal agents.

It is another object of the present invention to provide pesticidal, forexample insecticidal and acaricidal, preparations or formulationscontaining novel organic phosphorus diacid ester dimethyl thioethers,which possess highly effective pesticidal, especially insecticidal andacaricidal, properties with regard to use in connection with pestcontrol, mainly in plant protection and in the field of hygiene.

It is another object of the present invention to provide particularorganic phosphorus diacid ester dimethyl thioethers of the foregoingtype which possess a comparatively low toxicity toward warm-bloodedanimals, yet which possess a good compatibility with respect to plants.

It is still another object of the present invention to providecompositions or formulations of such organic phosphorus diacid esterdimethyl thioethers with carrier vehicles, especially dispersible solidand liquid carrier vehicles.

It is still another object of the present invention to provide organicphosphorus diacid ester dimethyl thioethers of the foregoing type andcompositions or formula- Patented Sept. 17, 1968 tions thereof withcarrier vehicles, and/or with other known agriculturally beneficial,plant treating agents, for example plant protective agents, aspesticidal agents for the treatment of plants to guard against pestblight, etc., to which such plants may be susceptible.

It is a still further object of the present invention to provide aprocess for producing such organic phosphorus diacid ester dimethylthioethers, and methods for using such thioethers, and more specificallymethods for combatting pests such as insects and acarids, by applying toplants susceptible to damage by such pests, a pesticidally effectiveamount of such thioethers.

Other and further objects of the present invention will become apparentfrom the within specification and accompanying examples.

It has been found in accordance with the present invention thatcompounds of the above constitution are obtained in a smooth reactionand with very good yields, when u,a'-dihalo-dimethyl thioethers of thegeneral formula in which Hal represents a halogen atom and X has theforegoing meaning, are reacted with thionothiol-phos phoric(-phosphonic, -phosphinic) acids of the general formula P-S-H (III) inwhich R and R have the foregoing meaning, either in the form of theiralkali metal salts, such as sodium, potassium, and lithium salts, orammonium salts, or in the presence of acid-binding agents. Alkali metalcarbonates or alcoholates, such as sodium, potassium, andlithiumcarbonates or -alcoholates, including especially alkylolates, andparticuarly C -C lower alkanolates, are primarily suitable asacid-binding agents.

The process of the present invention proceeds according to the followingequation:

In the last-mentioned formulae, the symbols R, R and X have the meaninggiven above, while Hal represents a halogen atom, and M represents analkali metal such as sodium, potassium or lithium, or the ammoniumgroup. The reaction according to the present invention is preferablycarried out in the presence of inert organic media such as solvents ordiluents. Lower aliphatic ketones, and especially di-C -C alkyl ketones,such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methylisobutyl ketone as well as lower aliphatic nitriles and especially C -Calkane cyanides, e.g., aceto and propionitrile, have chiefly provedsatisfactory for this purpose.

Furthermore, it is expedient to carry out the reaction at roomtemperature or moderately elevated temperature (for examplesubstantially from about 20 to C.), preferably at the boilingtemperature of the mixture and, after combining the starting components,to continue heating the reaction mixture or some time (for examplesubstantially from about 1 to 3 hours), while stirring.

The a,a-dihalo-dimethyl thioethers required as starting materials, whichare not yet known from the literature, can be prepared according tomethods known in principle, by halogenation, especially chlorination orbromination, of the corresponding dicarbalkoxy- (especially di-C -Clower carbalkoxy-, i.e., dicarbo-C C lower alkoxy-) dicarbonamido-,dicarbo-N-alkylamido-(especially dicarbo- N-C C lower alkyl amido-),dicarbo N,N-dialkylamido- 4 chloro-ot,e dicarbethoxy-dimethyl thioetherdistills over under a pressure of 2 mm. Hg at 146 to 148 C. The compoundhas the refractive index 11 1.4865. The yield amount to 215 g. (78% ofthe theoretical).

Analysis.Calculated for a molecular weight of 275: S, 11.64%; Cl, 2.58%.Found: S, 12.06%; Cl, 25.73%. i I (C H O)gP-SCHSCIIS1 (OCzHs):

OOCzHs 000 11 p y b 1 4 yl f (b) 55 grams ofa,a-dichloro-ot,ot-dicarbethoxy-di dicyanodimelhyl thioethers,Preferably 111 an Inert Q g methyl thioether dissolved in 100 cc. ofacetonitrile are Solvent u h a an afomatlc hydfocflfbon, p y a addeddropwise at boiling temperature to a solution of mononuclear yhydrocarbgm having 6 ring carbon 81 g. 9.4 mol) of the ammonium salt of0,0-diethylatoms befllenes, f a clllorlnated hydrocarbon, p 15 thionthiol-phosphoric acid in 600 cc. of acetonitrile. The allly ed l f g t ip ifi lk l i ih -f l r 52; reaction InlXtFIe is sutlzsequently furltherlrileated at boiling C on an e Ofoei Y @116, c 0r ca temperature or oneour to comp ete t e reaction and, tetrachloride, triandtetrachloroethane, etc. The reaction after li to c poured i 2 li ofwater, Th is Preferably carried out at the boiling temperature ofseparated oil is taken up with methylene chloride, the the reactionmixture which is subssequently further heated 20 methylene hl id l i i di d d h Solvent di for about one hour. Tl l products am usuallycolorless tilled off. The residue is finally freed from the lastvolatile oils which can be disti ed in a vacuum. components at a bathtemperature of 50 to 60 C. under The thionothiol'phosphofic ('P -P -Pstrongly reduced pressure. The yield amounts to 110 g. acid estersproduced therefrom according to the present in- (96% f th the reti l),The '-bis-(0,0-diethyl- VefltiOIl are mostly Obtained in the form of anOil Well, thionothiol-phosphoryl)-ot,ot'-dicarbethoxy-dimethyl thiobutin general, such acid esters cannot be distilled withether has the ef tiindex 4 1525 out decomposition, even under strongly red d Pres-Analysis-Calculated for a molecular weight of 574: sure. Nevertheless,the acid esters can be freed from P, 10.8%; S, 27.90%. Found: P, 10.8%;3, 28.48%. t 1 volatile Components by prolonied 5 a On rats per os theproduct has a mean toxicity (DL about 50 to 60 C. in a vacuum, and can tus e puri e of 250 mg. per kg. animal weight.

The products of the present invention are distinguished EXAMPLE 2 by anoutstanding insecticidal and acaricidal activity. Moreover, theypossess, surprisingly and in contradistincz s fi 00 m tion to knowncompounds of analogous constitution, only a comparatively low toxicitytowards warm-blooded animals. Thus, the instant organic phosphorousdiacid ester $000M (IJOOFHS (VD dimethyl thioethers, i.e.,thionothiol-phosphoric acid es- 83 grflms (9- H101) 0f f Po s m Salt ofethyl-O- ters, thionothiol-phos-phonic acid esters, and thiono-pbos- 'PP ld ere dissolved in 600 phinic acid eesters of the foregoing type, maybe used to of aijetomtrlle, fi 55 g of 0:,0: -dichloro-ot,ot-dicarbcombat insect pests, such as the insects: beetles, bugs,GthPXYdImethYI thloethef f ss l d in 100 cc. of aceaphids, flies,mosquitoes, caterpillars, cockroaches as well tommle are added PP E toth'ls Solutlon at bolhl'lg as the acarids, mites and {iota temperature.The reaction mixture is subsequently heated The compounds which can beproduced according to at this temperature for a further hour, thencooled and the present invention are therefore used as pest controlPoured about 2 hues The Separated l 15 agents, mainly in plantprotection, and in the field of taker} "P 111 methylene chlorlde, the eyl l i hygiene for example to combat insects and acarids solution thendried and the solvent distilled off. The re- The following examples aregiven for the purpose f sidue is freed from volatile componentsdn avacuum. illustrating while not limiting, the present invention. TheYleld f f y 'p EXAMPLE 1 phonyl)-ot,ot-dicarbethoxy-dimethyl thioetheramounts to 0 102 g. (94% of the theoretical). The product has therefractive index 11, 15433. (12.33 2; me: P l'i lt s ti e a g S n 0; 0.01111 I a; .7 0. thioether are dissolved in 400 cc. of methylenechloride. o rats per 05 h mean t i i (131, of h This solution is m xed dI'OpWlS? with 270 g. o f sulfuryl pound i 50 Per kg, animalweight,chloride, the reaction mixture is heated at boiling tem- Th followingcompounds [c d-bis-(methyl-O-ethylstem; 131.322.33.32? .Eii"iii?2.in2; eS u et er an a,uis p eny- -et y -t ionothio-p osf l and the P1151156 15drled and fractwnally phonyl)-ot,a'-dicarbethoxy-dimethyl thioether(VIII)] can distilled. After evaporation of the solvent, the 0t,0L(-dlbeproduced in an analogous manner;

Toxicity towards Refractive warm-blooded Constitution index animals (DL[17.13 on rats per as in rug/kg.

(VII).-. CgH O S fi/OCzHs 1.5402 50 PSC|IH-S-CHS-P CH 0000,11, 00001115CH;

vIiI).. S 00 11 1. 5864 1,000

oiino ES COOC H 1 No symptoms.

5 EXAMPLE 3 v OOCHs JJOOCHQ (IX) (a) 540 grams of sulfuryl chloridedissolved in 500 cc. of methylene chloride are added dropwise to asolution of 356 g. (2 mole) of a,a'-dicarbomethoxy-dimethyl thioether in1000 cc. of methylene chloride. When the addition is completed, thereaction mixture is heated at boiling temperature for a further hour andthen fractionally distilled. 430 grams (76.5% of the theoretical) ofa,ot'-dichloro-a,a'-dicarbomethoxy-dimethyl thioether of RP. 140 C./2mm. Hg are obtained.

Analysis.Calculated for a molecular weight of 247: S, 12.96%. Found: S,13.44%.

UOOCH; OOCH:

(b) 61 grams (0.3 mol) of the ammonium salt of 0,0-diethyl-thionothiol-phosphoric acid are dissolved in 350 cc. ofacetonitrile. 37 grams of m,a-dichloro-u,a'-dicarb0- methoxy-dimethylthioether are then added dropwise to this solution at boilingtemperature. After stirring at the stated temperature for one hour, thereaction mixture is cooled and poured into water. The separated oil istaken up with methylene chloride, the methylene chloride solution isdried and the solvent distilled off. The residue is freed from volatilecomponents in a vacuum. The yield of cd-bis-(0,0-diethyl-thionothiolphosphoryl)-u,ot'-di carbomethoxy-dimethylthioether amounts to 80 g.

(97.5% of the theoretical), the refractive index 72 is 1.5320.

Analysis.-Calculated for a molecular weight of 546: P, 11.32%; S, 29.3%.Found: P, 11.34%; S, 29.21%.

On rats per os the compound has a mean toxocity (DL of 100 mg. per kg.animal weight.

The compound ned-bis-(ethyl-O-ethyl-thionothiolphosphonyl)-a,a-dicarbomethoxy-dimethylthioether of the following constitution 21 5 Is S OCgHs CgHi OOCH;1000113 02H!) can be obtained under analogous reaction conditions. Theproduct has the refractive index n;; 1.5528 and a mean toxicity on ratsper os of 50 mg. per kg. animal weight.

It may be seen from the foregoing that the various organic phosphorusdiacid ester dimethyl thioethers of the present invention may be usedper se or in the form of compositions or formulations with dispersiblecarrier vehicles to combat various pests, such as insects and acarids.The compounds and formulations in question give outstanding insecticidaland acaricidal effects. The compounds in question may be used in suchformulations with carrier vehicles in pesticidally, and more especiallyinsecticidally or acaricidally, effective amounts, and such amounts maybe generally between about 0.195% by weight of the mixture with thecarrier vehicle.

The compounds which may be used according to the present invention canbe utilized, if desired, in the form of the usual formulations withdispersible carrier vehicles, such as solutions, emulsions, emulsifiableconcentrates,

suspensions, spray powder, pastes, granulates, soluble powders, dustingagents, etc., and the like. These are prepared in known manner, forexample, by extending the active agents with dispersible carriervehicles such as solvents and/or solid carriers, optionally with the useof emulsifying agents and/or dispersing agents (cf. AgriculturalChemicals, March 1960, pages 35-38). The following can be chieflyconsidered as carrier vehicles or adjuvants for this purpose: solvents,such as aromatic hydrocarbons (for example, toluene, xylene or benzene,etc.), chlorinated aromatic hydrocarbons (for example, chlorobenzenes),parafiins (for example, petroleum fractions), alcohols (for example,methanol, propanol or butanol, etc.), amines (for example,ethanolamine), dimethyl-formamide, and water; finely divided solidcarriers, such as natural ground minerals (for example, kaolins,alumina, talc and chalk) and synthetic ground minerals (for example,highly dispersed silicic acid and silicates, e.g., alkali silicates,etc.); emulsifying agents, such as nonionic and anionic emulsifyingagents (for example, polyethylene oxide esters of fatty acids,polyethylene oxide ethers of fatty alcohols, alkyl sulfonates and arylsulfonates, especially magnesium stearate, sodium oleate, etc.); anddispersing agents, such as lignin, spent sulphite liquors and methylcellulose, etc.

Generally, the organic phosphorus diacid ester dimethyl thioethers ofthe type contemplated herein, 13., the thionothiol-phosphoric acidesters, thionothiol-phosphonic acid esters and thethionothiol-phosphinic acid esters, may be used in the form of theirformulations with carrier vehicles and/or other active agents, or in theform of particular dosages for specific application, etc., such as inthe physical form of powders, granulates, solutions, emulsions, orsuspensions. The application of the active pesticidal agent is carriedout in the usual manner, for example by spraying, atomizing, dusting,watering, etc. As examples for the special utility the followinginventive compounds have been tested with regard to their effectivenessagainst spider mites, caterpillars and aphids.

EXAMPLE A Tetranychus test Solvent: 3 parts by weight of acetoneEmulsifier: 1 part by weight of alkylaryloxypolyglycol ether To producea suitable preparation of active compound, 1 part by weight of theactive compound is mixed with the stated amount of solvent containingthe stated amount of emulsifier and the concentrate so obtained isdiluted with water to the desired concentration.

Bush beans (Phaseolus vulgaris), which have a height approximately 10-30cm., are sprayed with the preparation of the active compound untildripping wet. The bush beans are heavily infested with spider mites(Tetranychus telarius) in all stages of development.

After 48 hours the eifectiveness of the preparation of active compoundis determined by counting the dead mites. The degree of destruction thusobtained is expressed as a percentage: means that all the spider mitesare killed whereas 0% means none are killed.

The active compounds, their concentrations, and the results obtained canbe seen from the following Table l:

TABLE 1 Compound Concentration of Degree of destruc- No. Active Agent(Constitution) active agent in tion of pests in percent percent (V) H H0. 001 100 (CzH5O)zP-S CII SCH SP(OCzH5)2 COOCzH5 COOCzH5 (VI) C 1H5O\fii Calls 0. 001 100 P- S -C H S C H S P l 02115 00002115 00002115 C2H5(VII) CzH5O\fi i O C2H5 O. 001 100 P-S-CH S-(EH S-P CH; COOCzH5 COOCzHsCH EXAMPLE B of emulsifier and the concentrate is diluted to the desiredPlutella test Solvent: 3 parts by weight of acetone Emulsifier: 1 partby weight of alkylaryloxypolyglycol ether To produce a suitablepreparation of active compound, 1 part by weight of the active compoundis mixed with the stated amount of solvent containing the stated amountof emulsifier and the concentrate is diluted with water toconcentration.

Bush bean plants (Vicia faba) which have been heavily infested withblack bush bean aphids (Doralis fabae) are sprayed with the preparationof the active compound until dripping wet.

After 24 hours the degree of destruction is determined as a percentage:100% means that all the aphids are killed whereas 0% means that none arekilled.

The active compounds, their concentrations, and the reh d i dconcentration, sults obtained can be seen from the following Table 3:

TABLE 3 Compound Concentration of Degree of destruc- N 0. Active Agent(Constitution) active agent in tion of pests in percent percent (X) |S i0.01 100 (G H O) P-SCH S-(EH S-P(OCzHs):

000cm oooon;

(XI) 021150 S S O 02H; 0. 004 95 ll P-S(llI-I SCH S-P CzHs COOCH; COOCH:C 115 Cabbage leaves (Brassica oleracea) are sprayed with thepreparation of the active compound until dew moist and are then infestedwith caterpillars of the diamondback moth (Plutella maculipennis).

After 4 days the degree of destruction is determined as a percentage:100% means that all the caterpillars are killed whereas 0% means thatnone are killed.

The active compounds, their concentrations, and the results obtained canbe seen from the following Table 2:

Preferably, as used herein, both the specification and claims, thesymbols R and R each include as the case may be, lower alkyl groups,preferably C -C alkyl groups or lower alkoxy groups, preferably C -Calkoxy groups such as methyl, ethyl, n propyl, isopropyl, n-butyl,isobutyl, sec.-butyl, tert.-butyl, and the like as well as methoxy,ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec.-butoxy,tert.-butoxy, and the like, as well as the phenyl group.

TABLE 2 Compound Concentration of Degree of destruc- N 0. Active Agent(Constitution) active agent in tion of pests in percent percent (VII)C2H5U\fi ISI/ 0 02H: 0. 001

P-S--C|J H SCH-SP\ CH3 COOCZH5 COOCzHs CH5 (XI) CzHsO 8 IS 0 02115 0.00170 P-S-CH S-C H SP C 11 COOCH; COOCH; C1115 EXAMPLE C In the same way, Xas used herein, both in the specifi- Emnlsifier: 1 part by weight ofalkylaryloxypolyglycol ether To produce a suitable preparation of activecompound, 1 part by weight of the active compound is mixed with thecation and claims, includes especially lower carboalkoxy, such as C -Clower carboalkoxy, i.e., carbo C -C lower alkoxy, such as carbomethoxy,carboethoxy, carbo-n-propoxy, carboisopropoxy, carbo-n-butoxy,carbo-isobutoxy, carbo-sec.-butoxy, and carbo-tert.-butoxy.

Especially contemplated herein are those thioethers in which X is lowercarboalkoxy, and in which R and R are both alkoxy, or in which R isalkoxy and R is alkyl, or

stated amount of solvent containing the stated amount in which R isalkoxy and R is phenyl. More specifically,

9 a,u bis(0,0 diloweralkyl thionothiol phosphoryl)- et,oc"diWe1'carboalkoXy-dimethyl thioethers having th formula S I [(lower alkoxy) zlS CH (lower carboalko y) ]:S

and a,a-bis-(lower alkyl-O loweralkyl-thionothiol-phosphonyl)-a,a'-dilower carboalkoxy-dirnethylthioethers having the formula lower alkoxy\fi P S C H (lowercarboalkoxy) 28 lower alkyl as well as u,u'-bis-(phenyl-O-loweralkyl-thionothiol-phosphonyl-a,a'-dilower carboalkoXy-dimethylthioethers having the formula lower alkoxy S PSCH(lower carboalkoxy) 2 Sphenyl in which R and R each respectively represents a member selectedfrom the group consisting of lower alkyl, lower alkoxy, and phenyl, andX represents lower carboalkoxy.

2. Thioethers according to claim 1 wherein X is C -C lower carboalkoxy,and R and R are C -C alkoxy.

3. Thioethers according to claim 1 wherein X is C -C lower carboalkoxy,R is C C/ alkoxy, and R is C -C alkyl.

4. Thioethers according to claim 1 wherein X is C -C lower carboalkoxy,R is C -C alkoxy, and R' is phenyL 5.u,a'-Bis-(0,0-diloweralkyl-thionothiol-phosphoryl)-a,a'-dilowercarboalkoxy-dimethyl thioether having the formula II [(loweralkoxy) P- S C H (lower carboalkoxy)]zS 6. a,a-Bis-(loweralkyl-O-loweralkyl-thionothiolphosphonyl)-a,a'-dilowercarboalkoxy-dirnethylthioether having the formula loweralkoxy lower alkyl s -C H(lowercarboalkoxy):lzs

10 7. ot,ot' Bis-(phenyl-O-loweralrkyl-thiono thiolphosphornyl)-a,a'-dilowercarboalkoxy-dimethyl thioether having the formulapheuyl 8. a,oc'Bis-(0,0-diethyl-thionothiol-phosphoryl)-a,adicarboethoxy-dimethylthioether having the formula (C HzHa) i S -C H S -CH S (O C 2115):

OOCgH JOOCQH 9.a,a'Bis-(ethyl-O-ethyl-thionothiol-phosphonyl)-a,adicarboethoxy-dimethyl thioether having the formula C 2 S S I H /PS-CH-S CHS P\C2115 430002115 470002135 02115 10. 42,11Bis-(methyl-O-ethyl-thionothiol-pho'sphonyl)- a,u-dicarboethoxy-dimethylthioether having the formula 11. u,a'Bis-(phenyl-O-ethyl-thionothiol-phosphonyl)- u,a-dicarboeth-oxy-dimethylthioether having the formula CzHrO S s 002115 OOCzHs (JJOOCQHS 12.od-Bis-(0,0-diethyl-thionothiol-phosphoryl)-a,a-

dicarbomethoxy-dimethyl thioether having the formula H i (C HO)zPSCHS-CHS -P 0 0211 0 0 0 Ha 0 0 CH3 13. ec,ot' Bis(ethyl-O-ethyl-thionothiol-phosphonyl) a,adicarbomethoXy-dimethylthioether having the formula CzHaO S S OOOHa JOOCHa CzI-Is ReferencesCited UNITED STATES PATENTS 3,018,301 1/1962 Schrader 260929 CHARLES B.PARKER, Primary Examiner.

A. H. SUTTO, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,402,224 September 17, 1968 Hans-Gerd Schicke It is certified thaterror appears in the above identified patent and that said LettersPatent are hereby corrected as shown below:

Column 2, lines 50 to 34, formula III should appear as shov below:

P-S-H Column 3, line 12, "dicyanodimethyl" should read dicyano -dimethylline 25, before "well" insert as line 60, "a,a(-di" should read a,a -diColumn 4, line 1, "chloro-a-a-dicarbethoxy-dimethyl thioether" shouldread chloro-a-afidicarbethoxy-dimethyl thioether line 5 "Cl 2.58%"should read Cl, 25.8% line 15, "thionithiolphosphoric" should readthionothiol-phosphoric Column 9,

lines 51 to 53, the formula should appear as shown below:

S H [(lower alkoxy) P-SCH(1ower carboalkoxy)-] S Column 10, lines 11 to14, the formula should appear as shown below:

5 5 II II COOC H COOC H same column 10, lines 33 to 37, the left-handportion of the formula should appear as shown below:

C H O S Signed and sealed this 10th day of March 1970.

(SEAL) Attest:

Attesting Officer Commissioner of Patents

